Photochromism in p-methylbenzoylthioacetone and related β-thioxoketones

Alexander Gorski, Yevgen Posokhov, Bjarke Knud Vilster Hansen, Jens Spanget-Larsen, Jan Jasny, Fritz Duus, Poul Erik Hansen, Jacek Waluk

Publikation: Bidrag til tidsskriftTidsskriftartikelForskningpeer review

Resumé

Irradiation of p-methylbenzoylthioacetone with UV or visible light brings about spectral changes characteristic for the photochromic behavior of β-thioxoketones. The nature of the initial species and of the photochromic product can be assigned based on spectral studies of the electronic and IR spectra in rare gas matrices combined with quantum chemical calculations. Additional arguments for the vibrational assignments are provided by using polarized light to induce the phototransformation, and by subsequent measurements of linear dichroism on partially aligned samples. Comparison with the results previously obtained for three related molecules: thioacetylacetone, p-methyl(thiobenzoyl)acetone, and monothiodibenzoylmethane reveals a common pattern of the photochromic reaction. In all four molecules, the initial species corresponds to an intramolecularly hydrogen-bonded enolic molecular structure, and the main photochromic product to an "open", nonchelated enethiolic counterpart. On the basis of a computational TD-DFT study of ground and excited electronic states, possible mechanisms of the photochromic transformation are discussed.
OriginalsprogEngelsk
TidsskriftChemical Physics
Vol/bind338
Udgave nummer1
Sider (fra-til)11-22
Antal sider12
ISSN0301-0104
DOI
StatusUdgivet - 2007

Citer dette

Gorski, Alexander ; Posokhov, Yevgen ; Hansen, Bjarke Knud Vilster ; Spanget-Larsen, Jens ; Jasny, Jan ; Duus, Fritz ; Hansen, Poul Erik ; Waluk, Jacek. / Photochromism in p-methylbenzoylthioacetone and related β-thioxoketones. I: Chemical Physics. 2007 ; Bind 338, Nr. 1. s. 11-22.
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title = "Photochromism in p-methylbenzoylthioacetone and related β-thioxoketones",
abstract = "Irradiation of p-methylbenzoylthioacetone with UV or visible light brings about spectral changes characteristic for the photochromic behavior of β-thioxoketones. The nature of the initial species and of the photochromic product can be assigned based on spectral studies of the electronic and IR spectra in rare gas matrices combined with quantum chemical calculations. Additional arguments for the vibrational assignments are provided by using polarized light to induce the phototransformation, and by subsequent measurements of linear dichroism on partially aligned samples. Comparison with the results previously obtained for three related molecules: thioacetylacetone, p-methyl(thiobenzoyl)acetone, and monothiodibenzoylmethane reveals a common pattern of the photochromic reaction. In all four molecules, the initial species corresponds to an intramolecularly hydrogen-bonded enolic molecular structure, and the main photochromic product to an {"}open{"}, nonchelated enethiolic counterpart. On the basis of a computational TD-DFT study of ground and excited electronic states, possible mechanisms of the photochromic transformation are discussed.",
author = "Alexander Gorski and Yevgen Posokhov and Hansen, {Bjarke Knud Vilster} and Jens Spanget-Larsen and Jan Jasny and Fritz Duus and Hansen, {Poul Erik} and Jacek Waluk",
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Photochromism in p-methylbenzoylthioacetone and related β-thioxoketones. / Gorski, Alexander; Posokhov, Yevgen; Hansen, Bjarke Knud Vilster; Spanget-Larsen, Jens; Jasny, Jan; Duus, Fritz; Hansen, Poul Erik; Waluk, Jacek.

I: Chemical Physics, Bind 338, Nr. 1, 2007, s. 11-22.

Publikation: Bidrag til tidsskriftTidsskriftartikelForskningpeer review

TY - JOUR

T1 - Photochromism in p-methylbenzoylthioacetone and related β-thioxoketones

AU - Gorski, Alexander

AU - Posokhov, Yevgen

AU - Hansen, Bjarke Knud Vilster

AU - Spanget-Larsen, Jens

AU - Jasny, Jan

AU - Duus, Fritz

AU - Hansen, Poul Erik

AU - Waluk, Jacek

PY - 2007

Y1 - 2007

N2 - Irradiation of p-methylbenzoylthioacetone with UV or visible light brings about spectral changes characteristic for the photochromic behavior of β-thioxoketones. The nature of the initial species and of the photochromic product can be assigned based on spectral studies of the electronic and IR spectra in rare gas matrices combined with quantum chemical calculations. Additional arguments for the vibrational assignments are provided by using polarized light to induce the phototransformation, and by subsequent measurements of linear dichroism on partially aligned samples. Comparison with the results previously obtained for three related molecules: thioacetylacetone, p-methyl(thiobenzoyl)acetone, and monothiodibenzoylmethane reveals a common pattern of the photochromic reaction. In all four molecules, the initial species corresponds to an intramolecularly hydrogen-bonded enolic molecular structure, and the main photochromic product to an "open", nonchelated enethiolic counterpart. On the basis of a computational TD-DFT study of ground and excited electronic states, possible mechanisms of the photochromic transformation are discussed.

AB - Irradiation of p-methylbenzoylthioacetone with UV or visible light brings about spectral changes characteristic for the photochromic behavior of β-thioxoketones. The nature of the initial species and of the photochromic product can be assigned based on spectral studies of the electronic and IR spectra in rare gas matrices combined with quantum chemical calculations. Additional arguments for the vibrational assignments are provided by using polarized light to induce the phototransformation, and by subsequent measurements of linear dichroism on partially aligned samples. Comparison with the results previously obtained for three related molecules: thioacetylacetone, p-methyl(thiobenzoyl)acetone, and monothiodibenzoylmethane reveals a common pattern of the photochromic reaction. In all four molecules, the initial species corresponds to an intramolecularly hydrogen-bonded enolic molecular structure, and the main photochromic product to an "open", nonchelated enethiolic counterpart. On the basis of a computational TD-DFT study of ground and excited electronic states, possible mechanisms of the photochromic transformation are discussed.

U2 - 10.1016/j.chemphys.2007.07.030

DO - 10.1016/j.chemphys.2007.07.030

M3 - Journal article

VL - 338

SP - 11

EP - 22

JO - Chemical Physics

JF - Chemical Physics

SN - 0301-0104

IS - 1

ER -